Pesticidal o-ethyl-S-propyl-dithiophosphoric acid phenyl or naphthyl esters

ABSTRACT

O-ethyl-S-n-propyl-dithiophosphoric acid phenyl or naphthyl esters, i.e., O-ethyl-S-n-propyl-O- or S- optionally substituted phenyl or naphthyl-phosphorothionothiol- or dithiolates, of the formula   in which X is an oxygen or sulfur atom, and Z is a group of the formula   Y is a halogen atom or a lower alkyl, lower alkoxy, lower alkylmercapto, lower alkylsufinyl, nitro, cyano or phenyl group, and M IS 0, 1, 2 OR 3, WHICH POSSESS INSECTICIDAL, ACARICIDAL AND NEMATOCIDAL PROPERTIES.

United States Patent [191 Kishino et al.

14 1 Aug. 5, 1975 PESTICIDAL O-ETHYL-S-PROPYL-THIONOTHIOL ORDITHIOPHOSPHORIC ACID PI-IENYL OR NAPHTHYL ESTERS [75] Inventors: ShigeoKishino; Akio Kudamatsu;

Iwao Takase; Kozo Shiokawa; Shin-Ichi Yamaguchi, all of Tokyo, Japan[73] Assignee: Bayer Aktiengesellschaft,

Leverkusen, Germany- [22] Filed: May 17, 1974 [21] Appl. No.: 471,081

Related US. Application Data [62] Division of Ser. No. 123,087, March10, 1971, Pat.

[30] Foreign Application Priority Data Mar. 13, 1970 Japan 45-20845 [52]US. Cl. 424/225; 424/210; 424/216;

424/217; 424/218 [51] Int. Cl AOln 9/36 [58] Field of Search 424/225[56] References Cited UNITED STATES PATENTS 3,732,341 5/1973 Sirrenberg260/950 FOREIGN PATENTS OR APPLICATIONS 9/1963 Japan 260/964 PrimaryExaminer-Albert T. Meyers Assistant Examiner-Leonard Schenkman Attorney,Agent, or FirmBurgess, Dinklage & Sprung [57] ABSTRACTO-ethyl-S-n-propyl-dithiophosphoric acid phenyl or naphthyl esters,i.e., O-ethyl-S-n-propyl-O- or S- optionally substituted phenyl ornaphthyl-phosphorothionothiolor dithiolates, of the formula in which Xis an oxygen or sulfur atom, and Z is a group of the formula 9 Claims,No Drawings PESTICIDAL O-ETHYL-S-PROPYL-THIONOTHIOL OR DITHIOPHOSPHORICACID PHENYL OR NAPHTHYL ESTERS This is a division, of application Ser.No. 123,087, filed Mar. 10. 1971, now US. Pat. No. 3,825,636.

The present invention relates to and has for its objects the provisionof particular new O-ethyl-S-npropyldithiophosphoric acid phenyl ornapthyl esters, i.e., O-ethyl-S-n-propyl-O- or S-optionally substitutedphenyl or naphthyl-phosphorothionethiolor dithiolates, which possessinsecticidal, acaricidal and nematocidal properties, active compositionsin the form of mixtures of such compounds with solid and liquiddispersible carrier vehicles, and methods for producing such compoundsand for using such compounds in a new way especially for combatingpests, e.g., insects, acarids and nematodes, with other and furtherobjects becoming apparent from a study of the within specification andaccompanying examples.

In an agriculture, especially the cultivation of riceplants, the damagecaused by larvae of insects belonging to the Lepidoptera, such as therice stem borer (C/zilo suppressalis) and yellow rice borer (Trypoiyzaincertulas), and mites is a serious problem.

Much research has been directed to the control of these harmfulcreatures but only several pesticides among commercially availablepesticides are effective against them; almost all of these pesticidescomprise organic phosphorus compounds. Further, since the sameinsecticides have been used in great amounts, there has been a tendencyfor the harmful insects to acquire resistance to these insecticides.

The present invention provides phosphoric acid esters of the generalformula:

S a i-. I.

P-X-Z (l) nC, H S

in which X is an oxygen or sulfur atom, and Z is a group of the formulac ical (Ha) (11b) in which Y is a halogen atom or a lower alkyl, loweralkoxy,

lower alkylmercapto, lower alkylsulfinyl, nitro, cyano or phenyl group,and

m is O, l, 2or 3.

Although Y may be a fluorine or iodine atom, the preferred halogens arechlorine and bromine. Preferred lower alkyl and alkoxy groupsinclude-those with an alkyl moiety of l to 4 carbon atoms, namelymethyl, ethyl, nand iso-propyl and n-, iso-, secand tert-butyl.

When the compounds of this invention are compared with known compoundshaving analogous structures and compounds having similar directions ofbiological activity, the compounds of this invention are characterizedby substantially improved effects and very low toxicity to warm-bloodedanimals and hence, they are of great utility.

The compounds of this invention can be used for controlling harmfulinsects of a broad range such as harmful sucking insects, biting insectsand plant parasites.

They are especially effective as pesticides against insects harmful toagriculture, such as insects belonging to the Coleoptera, Lepidoptera,Aphidae, Orthoptera, lsoptera and Acarina as well as Nematodes living onplant and soil, and they can be used as agents for protecting plantsfrom such creatures.

The compounds of this invention exhibit a more pronounced insecticidalactivity than analogous compounds against insects belonging to theLepidoptera, whose control has been difficult by the conventionalinsecticides. Further, they exhibit a very high insecticidal activityagainst insects which have acquired resistance to thephosphorous-compound insecticides of the prior art. Still further, theyare effective for controlling rice stem borers. The compounds of theinvention have a very low toxicity and, in particular, do not exhibitsuch an acute toxicity to humans as is possessed by parathion andmethylparathion. Nevertheless, the insecticidal activity of thecompounds of this invention is comparable or superior to that ofparathion and, therefore, they can safely be used as agriculturalchemicals.

The present invention also provides a process for the preparation of acompound of the formula (I) in which (a) a thionophosphoric acid diesterhalide of the general formula (III) is reacted with a mercaptan of thegeneral formula MSC H -n or (b) a compound of the general formula c n o5 r1 /P-)( n-C H S S-R is reacted with a suitable oxidizing agent,preferably hydrogen peroxide,

in which formulae Hal is a halogen, preferably a chlorine, atom,

M is hydrogen atom or an alkali metal atom,

R is a lower alkyl group, and

X, Y, Z and m have the meaning stated above.

As suitable thionophosphoric acid diester monohalides, of the formula(III), the following may be cited:

O-ethyl-O-phenyl-thionophosphoric acid chloride,

O-ethyl-O-( 2-chlorophenyl )-thionophosphoric acid chloride,

O-ethyl-O-(4-chlorophenyl)-thionophosphoric acid chloride,

O-ethyl-O-(4-bromophenyl)-thionophosphoric acid chloride,

O-ethyl-O-( 2,4-dichlorophenyl )-thionophosphoric acid chloride,

O-ethyl-O-(2-chloro-4-tert-butylphenyl)- O-ethyl-O-( 4-cyanophenyl)-thionophosphoric 'thionophosphoric acid chloride,

O-ethyl-O-( 3,5dimethyl-4-chlorophenyl thionophosphoric acid chloride,

O-ethyl-O-( 2,4dichloro-6-methylphenyl thionophosphoric acid chloride,

O-ethyl-O-( 4-methoxyphenyl )-thionophosphoric acid chloride,

' O -ethyl-O-( 4-methylmercaptophenyl thionophosphoric acid chloride,O-ethyl-O-(2-methyl-4-methylmercaptophenyl)-.

thionophosphoric acid chloride,

O-ethyl-O 3-me'thyl4-methylmercaptophenyl)- thionophosphoric acidchloride, O-ethyl-O-(4-methylsulfinylphenyl)- thionophosphoric acidchloride, O'-ethyl-O-( 3methyl-4-methylsulfinylphenyl thionophosphoricacid chloride, Oethyl-O-( Z-nitrophenyl thionophosphoric chloride,O-ethyl-O-(4-nitrophenyl)-thionophosphoric chloride, O-ethyl-O-(3-chloro-4-nitrophenyl thionophosphoric acid chloride, O ethyl-O-(3-nitro-4-chlorophenyl thionophosphoric acid chloride, O-ethyl-O-(2-chloro-4-nitrophenyl thionophosphoric acid chloride, O-ethylO-(3-methyl-4-nitrophenyl thionophosphoric acid chloride,

acid

acid

acid

chloride,

O-ethyl-O-( 4-biphenyl)-thionophosphoric acid chloride,

Oethyl-O-(2-chloro-4-biphenyl)-thionophosphoric acid chloride,

O-ethyl-O-( alpha-napthyl )-thionophosphoric acid chloride,

O-ethyl-O-( beta-napthyl )-thionophosphoric acid chloride,

O-ethyl-O( l-bromo-beta-naphthyl v thionophosphoric acid chloride,

O-ethyl-O-(2,4dichloro-alpha-naphthyl)- thionophosphoric acid chloride,

O-ethyl-S-phenyl-thionophosphoric acid chloride, vO-ethyl-S-(4-chlorophenyl )-thionophosphoric acid chloride,

' O-ethyl-S-( 2,5-dichlorophenyl )-thionophosphoric acid chloride, and

' O-ethyl-S-(4-methylphenyl)-thionophosphoric acid chloride. In processvariant (a), the reaction is preferably effected in a solvent, whichterm herein includes a mere diluent. Any inert solvent may be used forthis purpose, for example water, aliphatic and aromatic hydrocarbonswhich maybe halogenated, such as methylene chloride, di-, triandtetra-chloroethylenes, chloroform, carbon tetrachloride, benzine,benzene, chlorobenzene, toluene and xylene; ethers such as diethylether, di-n-butyl ether, dioxane and tetrahydrofuran; low-boilingaliphatic ketones and nitriles such as acetone, methylethylketone,methylisopropylketone, methylisobutylketone, acetonitrile andpropionitrile; and low-boiling aliphatic alcohols such as methanol,ethanol and isopropanol.

The reaction of process variant (a) may be carried out in the presenceof an acid-binder according to need, usually when M is a hydrogen atom.Suitable acid-binders are hydroxides, carbonates, bicarbonates andalcoholates of alkali metals and tertiary organic bases such astriethylamine, dimethylaniline and pyridine. When the-reaction iscarried out in the absence of acid-binder, the intended product of highpurity can be obtained in high yield by-first forming an alkali metalsalt of n-propylmercaptan and then reacting the salt with the phosphoricacid diester mono-halide.

The reaction of process variant (a) may be effected at temperatures of afairly broad range, but generally the reaction is carried out at from20C to the boiling point of the reaction mixture, preferably from 0 toC.

The process variant (b) is, of course, suitablefor the preparation onlyof those compounds of the formula (I) in which Z is a phenyl groupsubstituted by an alkylsulfinyl group, with m being, therefore,'at least1.

The reaction of process variant (b) is preferably effected in a solvent,for example one of these mentioned fected at 0 to 100C.

The active compounds according to the instant invention can be utilized,if desired, in the form of the usual formulations or compositions withconventional inert (i.e., plant compatible or herbicidally inert)pesticide diluents or extenders, i.e., diluents, carriers or extendersof the type usable in conventional pesticide formulations, preparationsor compositions, e.g., conventional pesticide formulations, preparationsor compositions such as solutions, emulsions, suspensions, emulsifiableconcentrates, wettable powders, soluble powders, oils, aerosols, pastes,fumigating powders, dusting powders, granules, pellets and tablets, etc.These are formulated or prepared in known manner, for instance by mixingthe active compounds with conventional pesticide dispersible liquid orsolid diluent, carriers or extenders optionally with the use of carriervehicle assistance, e.g., conventional pesticide surface-active agents,including emulsifying agents 'adhesive agent and/or dispersing agents,whereby, for example, in the case where water is used as diluent,organic solvents and/or surfactants may be added as auxiliary solvents.

The following may be chiefly considered for use as conventional carriervehicles for this purpose: aerosol propellants which are gaseous atnormal temperatures and pressures, such as freon; inert dispersibleliquid diluent carriers, including inert organic solvents, such asaromatic hydrocarbons (e.g. benzene, toluene, xylene, aromatic naphtha,dimethyl naphthalene, etc.), halogenated, especially chlorinatedaromatic hydrocarbons (e.g. chlorobenzenes, etc.), aliphatichydrocarbons (e.g. benzine, cyclohexane, paraffms, petroleum fractions),chlorinated aliphatic hydrocarbons (e.g. methylene chloride, ethylenechloride, etc.), alcohols (e.g. methanol, ethanol, propanol, butanol,etc.), amines (e.g. ethanolamine, etc.), ethers, ether-alcohols, (e.g.glycol monomethyl ether, etc.), amides (e.g. dimethyl formamide, etc.),sulfoxides (e.g. dimethyl sulfoxide, etc.), ketones (e.g. acetone,methylethyl ketone, cyclohexanone, etc.) and/or water; as well as inertdispersible finely divided solid carriers, such as ground naturalminerals (e.g. clays, talc, pyrophyllite, mica, gypsum, calcite,vermiculite, dolomite, apatite, calucium or magnesium lime, diatomaceousearth, inorganic salts i.e. calcium carbanate, pumice, etc.) and groundsynthetic minerals (e.g. highly dispersed silicic acid, silicates, e.g.alkali silicates, etc.); whereas the following may be chiefly consideredfor use as conventional carrier vehicle assistants, e.g. surface-activeagents, for this purpose, emulsifying agents, such as non-ionic and- /oranionic and/or cationic emulsifying agents, (e.g. polyethyleneoxideesters of fatty acids, polyethylene oxide ethers of fatty alcohols,alkyl sulfonates, aryl sulfonates, alkyl dimethyl benzyl ammoniumchloride, etc., and especially alkyl arylpolyglycol ethers, magnesiumstearate, sodium oleate, etc.); and/or dispersing agents, such aslignin, sulfite waste liquors, methyl cellulose, etc.

Such active compounds may be employed alone or in the form of mixtureswith one another and/or with such solid and/or liquid dispersiblecarrier vehicles, optionally with the use of carrier vehicle assistantsand/or with other known compatible active agents, especially plantprotection agents, such as other insecticides, acaricides, nematocides,fungicides, bactericides, herbicides, rodenticides, fertilizers or plantgrowthregulating agents, etc., if desired, or in the form of particulardosage preparations for specific application made therefrom, such assolutions, emulsions, suspensions, powders, pastes, and granules whichare thus ready for use.

As concerns commercially marketed formulations, these generallycontemplate carrier composition mixtures in which the active compound ispresent in an amount substantially between about 0.1 95% by weight, andpreferably 0.5 90% by weight, of the mixture, whereas carriercomposition mixtures suitable for direct application or fieldapplication generally contemplate those in which the active compound ispresent in an amount substantially between about 0.0001 preferably 0.0015%, by weight of the mixture. Thus, the present invention contemplatesover-all compositions which comprise mixtures of a conventionaldispersible carrier vehicle such as (l) a dispersible inert finelydivided carrier solid, and/or (2) a dispersible carrier liquid such asan inert organic solvent and- /or water preferably including asurface-active effective amount of a carrier vehicle assistant, eg asurfaceactive agent, such as an emulsifying agent and/or a dispersingagent, and an amount of the active compound which is effective for thepurpose in question and which is generally between about 0.0001 95%, andpreferably 0.001 95%, by weight of the mixture.

The amount of active compound applied per unit area is usually about 150to 10,000 grams, preferably 400 to 6,000 grams of active compound perhectare.

However, in special cases, it may be possible to use more or less,sometimes such variations may be required.

The active compounds can also be used in accordance with the well knownultra-lowwolume process with good success, i.e., by applying suchcompound if normally a liquid, or by applying a liquid compositioncontaining the same, via very effective atomizing equipment, in finelydivided form, e.g. average particle diameter of from 50 100 microns, oreven less, i.e., mist form, for example by airplane crop sprayingtechniques. Only up to at most about a few liters/hectare are needed,and often amounts only up to about 150 to 10,000g/hectare preferably 400to 6,000g/hectare, are sufficient. In this process it is possible to usehighly concentrated liquid compositions with said liquid carriervehicles containing from about 20 to about by weight of active compoundor even the %active substance alone, e.g., about 20 100% by weight ofthe active compound.

Furthermore, the present invention contemplates methods of selectivelykilling, combating or controlling pests, e.g., arthropods, i.e., insectsand acarids, and more particularly methods of combating at least one ofinsects and acarids which comprises applying to at least one ofcorrespondingly (a) such insects, (b) such acarids, and (c) thecorresponding habitat thereof, i.e., the locus to be protected, acorrespondingly combative or toxic amount, i.e., an arthropodicidallyespecially insecticidally or acaricidally, effective amount of theparticular active compound of the invention alone or together with acarrier vehicle as noted above. The instant formulations or compositionsare applied in the usual manner, for instance by spraying, atomizing,vaporizing, scattering, dusting, watering, squirting, sprinkling,pouring, fumigating, and the like.

It will be realized, of course, that the concentration of the particularactive compound utilized in admixture with the carrier vehicle willdepend upon the intended application. Therefore, in special cases it ispossible to go above or below the aforementioned concentration ranges.

The unexpected superiority and outstanding activity of the particularnew compounds of the present invention are illustrated, withoutlimitation, by the following examples:

EXAMPLE 1 20.5 g of the sodium salt of n-propylmercaptan are suspendedin 100 ml of acetonitrile, and 61 g of O- ethyl-O-(2,4-dichlorophenyl)thionophosphoric acid chloride are added to the suspension dropwise at5l0C with vigorous agitation. The temperature is gradually raised to70C, and at this temperature the reaction is carried out for 3 hours.

Acetonitrile is removed from the reaction mixture by distillation andthe residue is dissolved in benzene, washed with water and 1% sodiumcarbonate and dried over anhydrous sodium sulfate. Distillation of thebenzene gives 55 g ofO-ethyl-O-(2,4-dichlorophenyl)-S-npropyl-phosphorothionothiolate of thefollowing formula:

7 The product has a boiling point of l64l67C under 0. l 8 mmHg and arefractive index n of l.5698. The compound is hereinafter identified ascompound No. 4.

EXAMPLE 2 The product has a boiling point of l55l58C under 0.1 mmHg anda refractive index n of 1.5859. The compound is hereinafter identifiedas compound No. 17.

8 EXAMPLE 3 32 g ofO-ethyl-O-(4-methylmercapto-phenyl)-S-npropylphosphorothionothiolate aredissolved in 150 mlof methanol. Several drops of 50% sulfuric acid areadded to the solution, and 12 g of aqueous hydrogen peroxide are addedthereto dropwise at 5l0C. The mixture is agitated for 1 hour and furtheragitation is conducted at C for 3 hours. A major portion of the methanolis removed by distillation and the residue is dissolved in benzene,washed with water and 1% sodium carbonate, and dried over anhydroussodium sulfate. Distillation of benzene gives 30 g of O-ethyl-O-(4-methylsulphinyl-phenyl )-S-n-propylphosphorothionothiolate of thefollowing formula:

GS-m3 11-63975 After the product has been subjected to columnchromatography with active alumina, it exhibits a refractive index n,,'-of 1.5820. The compound is hereinafter identified as compound No. 20.

EXAMPLE 4 The following compounds may be prepared by methods analogousto those described in Examples 1, 2 and Table l n -C H S PhysicalProperties Comx z Boiling Point or Refractive poun No. Melting Pointindex cl 131c/005 mmHg 1 2 0 D Y b.p. 136- k1,, 1.5620

l38C/0.08 mmHg 3 0 -c| b.p. 158- n 1.5601

l62C/O.l5 mml-lg I I Cl 5 0 l b.p. 150- 11,?" 1.5790

l52C/0.05 mmHg CI Cl 6 0 Q41 b.p. 145- 11,, 1.5737 G 14sc o.05 mmHg132c/0.05 mmHg Br 8 0 Br Cl 9 0 Q b.p. 14s- 11,?" 1.5972

CI l52C/0.07 mmHg 7 CH3 i 10 0 b.p. 134- n,,'- 1.5484

13sC/0.07 mmHg CH3 v 11 0 11 b.p. 12sn,,?",1.553o

l30C/0.07 mrnHg 12 0 )4: H mm b.p. 1 n 20 1.5391

c T 143c/0.05 mmHg 13 0 1 11,3 1.5412

EXAMPLE 5 parts ofcompound (28), 80 parts oldiatomaceous earth and clayand 5 parts of the emulsifier RUN- NOX (product of Toho Kagaku KogyoK.K., Japan) containing the active compound at a prescribedconcentration.

Test 1 Test on rice stem borers (C/zz'lo supperssalis) larvae are groundand mixed together to form a wettable pow- 5 der. It is diluted withwater for actual application. [dia- T procedure ggg igi y sgzg yigg :22:(32) RUNNOX Rice plants of tillering stage in a pot of 12 cm diameterare attached with eggs of rice stem borer. Seven EXAMPLE 6 10 days afterhatching, the preparation of the active com- 30 parts of compound (4),30 parts of Xylene 30 pound prepared in Example 9 at the prescribedconparts of KAWAKAZOL (product of Kawasaki Kasei cemmtlqn 1S Sprayed anamount of 40 ml per pot and gy K'Kq Japan) and 10 parts of theemulsifier the pot 18 then kept in greenhouse for 3 days. The (productof Toho Kagaku Kogyo KKI, stems of the so-treated rice plants areexamined sepap are mixed with stirring to for m an emulsifiable l5rately to count the numbers of l1v1ng nsects and dead concentration. Itis diluted with water for actual appli- Insects and to Calculate thekmmg ratlo' cation. [KAWAKAZOL: aliphatic hydrocarobons Test 2 with highboiling point; SORP L": polyoxyethylenealkylarylether] 20 Test ontobacco cutworm (Prodenza lztura) larvae:

EXAMPLE 7 Test procedure 10 parts ofcompound (36), 10 parts of bemonite,78 Sweet-potato leaves are dipped in a preparation of parts of talc and2 parts of lignin sulfonate are formed the F P prepare d m Example and xinto a mixture and it is intimately mixed with parts dned m placed m 9Cm d'ameter of water. The mixture is finely divided by means of an 25dlsh' l 10 thlrd'lnstar tob acco larvae extruding granulator to giveparticles of 20 40 mesh, are Put mto h l and the S' kept m a thermostatfollowed by drying at chamber maintained at 28 C. After 24 hours havepassed, the number of the dead larvae 1S counted and EXAMPLE 8 thekilling ratio is calculated.

2 parts of compound No. 17 and 98 parts ofa mixture 30 Test 3 of talcand clay were ground and mixed together to form a dust. [talc and clay(3:1)] Note: The term Test on almond moth p callfellflli parts used inthe Example (5) to (8). means weight. Tst procedure EXAMPLE 9 2Oalmond-moth mature larvae are put into a wire gauze vessel of 7 cmdiameter and 0.9 cm height. The Preparation of Test compound vessel isdipped for 10 seconds in a preparation of the active compound preparedin Example 9 at a pre- Solvent: 3 parts by weight of dim thylf n scribedconcentration, and then the vessel is allowed to Emulslfien Sale? by(fight of alkyl aryl polyglycol 40 stand for 24 hours in a thermostatchamber. The number of dead larvae is counted and the killing ratio iscal- I culated.

In order to prepare a suitable preparation of an active The results ofthe tests are shown in Table 2 in which compound, one part by weight ofthe active compound results of comparative tests using analogouscomis'mixed with the above amount of the solvent containpounds,designated compounds (A) to (L), are also ing the above amount of theemulsifier, and the mixture shown. The entries in the table are killingratios exis diluted with water to form an aqueous preparation pressed aspercentagevalues.

Table 2 Harmful Insects Compound Active Tobacco cutworm Almond moth ricestern Component borer Concentration 0.1% 0.03% 0.01% 0.1% 0.03% 0.01%0.03%

C H 0 I 2 .1 I (A) PC 0 0 0 O 0 2.5

cu .s

S C.,H-O ll n (B) PO 5 0 20 0 0 3.1

C H -,S

S 041 0 1| 1) PO-C 100 100 100 100 100 100 nC H;S

8 2 10 ll (0 P o-Q 100 15 0 100 80 15 12.3

Table 2 Continued Harmful Insects Compound Active Tobacco cutworm Almondmoth rice stem Component borer Concentration 0.1% 0.03% 0.01% 0.1% 0.03%0.01% 0.03%

CI CZHSO (D) Cl 70 0 50 0 0 0 C H,-,S

Cl C2H5O (4) Cl 100 100 100 100 100 100 100 nC -,H S

S Cl C2H -,O (E) p o c1 90 45 0 0 0 3.6

nC H ,S

0,11 0 (F) P-O @501 95 0 15 0 0 40 C2H -,S

S C-,H -,O 17) P-O Oscu 100 100 100 100 100 100 100 n-C 3H1S s C..H -,O(G) PO @404 100 80 0 75 0 0 19.2

n-C.,H,,S

0,11 0 (11) PO-cl so 0 0 0 0 1.1

CH,S

S C-,H,-,O (36) P s C| 100 100 100 100 100 100 100 n-C H S S C H O (J) 5P-s@cl 100 85 5 95 0 0 6.5

nC H S C- H O (K) 2 8O 10 0 60 0 u 3.2

c u s s Cal-l O 23 5 P o--cN 100 100 100 10 0 100 100 100 nC;,H S

S OH O (1. 5 P o-@-c 100 0 100 30 0 15.3 nC H S 7 Untreated control 5 58.-

From the results shown in Table 2 it can be seen that Table 3'-.Continued phosphoric acid esters of the formula (I) exhibit particularlyexcellentcffects against harmful insects belong- Results of Test ofEffect aga'ihs Tobacco Cutworm mg to the Lepidoptera as compared withanalogous 4 Killin Ratio compounds Compound No. 1000 ppm 300 ppm 100 ppmEXAMPLE 16 100 80 17 1 100 100 Test on Tobacco cutworm: 5O 18 100 100 l9l0() 100 90 Test Procedure 20 100 I00 [00 1 2 1 00 The test 1s conductedin the same manner as in Test 88 I i 2 of Example 9. The results areshown in Table 3. 23 100 100 100 24 100 100 100 Table 3 25 100 100 10026 100 100 100 27 100' lOO 100 Results of Test of Effect against theTobacco Cutworm 28 100 lOO 100 Killing Ratio 29 100- 100 100 CompoundNo. 1000 ppm 300 ppm 100 ppm 30 I00 100 100 3l I00 100 I00 1 100 100 10032 1 100 90 2 100 100 100 33 100 I00 100 3 100 100 100 34 100 0 77 4 100100 I00 35 100 100 100 5 100 100 0 36 100 100 100 6 lOO 100 100 37 I00100 80 7 lOO lOO lOO 38 I00 I00 60 8 100 I00 100 9 100 100 100 Sumithion(commercially 100 2O 10 100 100 60 available comparison) 11 100 100 5012 100 96 60 News; 13 100 100 The compounds num ers in the Tablecorrespond to those in Examples 1 7 and i4 90 80 3 dTlb| l 15 100 100100 A e 'Sumithion: 0,0-dimcthyl-O-( 3-methyl-4-nitrophcnyl)thiophosphutc 15 EXAMPLE 1 1 Test on carmine mites imagines (Tetranychustelarius). Test Procedure A haricot plant having two developing leavesplanted 5 in a 6 cm diameter pot is placed with 50-100 carmine miteimagines and nymphs. Two days after the infection, emulsions containingthe active compound at a prescribed concentration. which is prepared inthe same manner as in Example 9, is sprayed in an amount of 40 ml perpot. The pot is kept in a greenhouse for 10 days, and the control effectis evaluated. The evaluation is expressed by an index on the followingscale: Index:

3: No living imago or nymph.

2: less than 5% of living imagines and nymphs based on the untreatedcontrol l: 5 50% of living imagines and nymphs based on theuntreatedcontrol' 0: more than 50% of living imagines and nymphs basedon the untreated control. The results are shown in Table 4.

Table 4 Results of tests of effects against Carmine mites:

Control effect index 100 ppm Compound No. 300 ppm 36Phenkaptone(commercially available comparison) C PCBS (commerciallyavailable comparison) Notes:

The compound numbers in the Table correspond to those in Examples 1. 3and 3 and Table l. Phenkaptone: dithiophosphate CPCBS:p-ishlorophenyhp'-chlorobenzenesulfonate 0.0-diethyl-S-(2.5-dichlorophenylmcrcaptomethyl) 5O EXAMPLE 12 Test on green peachaphids (Myzus persica):

Test Procedure A sweet-potato leaf is dipped in an emulsion containingthe active compound at a prescribed concentration, which is prepared inthe same manner as inExample 9 1 and dried in air. Then the'leaf isplaced in a Petri dish 16 Table 5 Effects against green peach aphids:Compound No. Killing Ratio (7:)

Notes:

The compound numbers in the Table correspond to those in Examples 1. 2and 3 and Table l.

Disyston: 0.0-diethyl-S-2( ethylthio )phosphorodithioate Paruthion":0.0-diethybp-nitrophenyl-thiophosphate EXAMPLE 13' Preparation of testcompound 2 parts by weight of an active compoundis mixed with 98 partsby weight of talc, and the mixture is 5 ground to form a dust.

Test on root knot nematode disease (Meloidogyne Imp/t1):

Test Procedure The so-prepared dust is mixed, with soil tainted withsweet-potato root knot nematodes in an amount such that a prescribedconcentration of the active compound is attained in the soil. Thetreated soil is uniformly stirred and mixed, and then it is packed intopots each having an area of 1/5000 are. About 20 tomato seeds (Kuriharavariety) are sowed per pot and cultivated for 4 weeks in a greenhouse.Each root is then drawn out from the soil without harming it. The damagedegree is evaluated as the averageof l0 roots for each group, based onthe following scale.

Damage Degree no knot (perfect control) knots are formed slightly knotsare formed appreciably knots are formed considerably formation of knotsis extreme (same as in untreated control).

by the following equaavailable comparison) Notes:

The compound numbers in the Table correspond to those in Examples l. 2and 3 and Table l.

VC: 0.0-(1iethyl-O-diehlorophenylthiophosphate.

It will be appreciated that the instant specification and examples areset forth by way of illustration and not limitation, and that variousmodifications and changes may be made without departing from the spiritand scope of the present invention.

What is claimed is:

l. A method of combating insects, acarids and nematodes which comprisesapplying to the insects, acarids, nematodes or a habitat thereof aninsecticidally, acaricidally and nematocidally effective amount of aphosphoric acid ester of the formula in which X is an oxygen or sulfuratom, Z is a group of the formula Y is a halogen atom, lower alkyl, orphenyl, and

m is 0,1, 2 or 3.

2. The method of claim 1 wherein Y is chlorine, bromine, phenyl or C -Calkyl.

3. The method of claim 1 wherein said ester is O-ethyl-O-phenyl-S-n-propyl-phosphorothionothiolate of the formula 4. Themethod of claim 1 wherein said ester is O- ethyl-O-( 4-chlorophen yl)-S-n-propyl-phosphorothionothiolate of the formula 5. The method ofclaim 1 wherein said ester is O-ethyl-O-(2,4-dichlorophenyl)-S-n-propyl-phosphorothionothiolate of theformula 18 0 11 0 T & 1 n-C E S 6. The method of claim 1 wherein saidester is O- ethyl-O-( 2,4,5-trichlorophenyl)-S-n-propylphosphorothionothiolate of the formula] 7. The method ofclaim 1 wherein said ester is O-ethyl-S-(4-chlorophenyl)-S-n-propyl-phosphorothionodithiolate of theformula 8. An insecticidal, acaricidal and nematocidal compositioncomprising an insecticidally, acaricidally, and nematocidally effectiveamount of a phosphoric acid ester of the formula in which X is an oxygenor sulfur atom, Z is a group of the formula

1. A METHOD OF COMBATING INSECTS ACARIDS AND NEMATODES WHICH COMPRISESAPPLYING TO THE INSECTS, ACARIDS, NEMATODES OR A HABITAT THEREOF ANINSECTICIDALLY, ACARICIDALLY AND NEMATOCIDALLY EFFECTIVE AMOUNT OF APHOSPHORIC ACID ESTER OF THE FORMULA
 2. The method of claim 1 wherein Yis chlorine, bromine, phenyl or C1-C4 alkyl.
 3. The method of claim 1wherein said ester isO-ethyl-O-phenyl-S-n-propyl-phosphorothionothiolate of the formula 4.The method of claim 1 wherein said ester isO-ethyl-O-(4-chlorophenyl)-S-n-propyl-phosphorothionothiolate of theformula
 5. The method of claim 1 wherein said ester isO-ethyl-O-(2,4-dichlorophenyl)-S-n-propyl-phosphorothionothiolate of theformula
 6. The method of claim 1 wherein said ester is O-ethyl-O-(2,4,5-trichlorophenyl)-S-n-propyl-phosphorothionothiolate of the formulal 7.The mEthod of claim 1 wherein said ester isO-ethyl-S-(4-chlorophenyl)-S-n-propyl-phosphorothionodithiolate of theformula
 8. An insecticidal, acaricidal and nematocidal compositioncomprising an insecticidally, acaricidally, and nematocidally effectiveamount of a phosphoric acid ester of the formula
 9. The composition ofclaim 8 wherein the ester is:O-ethyl-O-phenyl-S-n-propyl-phosphorothionothiolate,-phenyl-S-n-propyl-phosphorothionothiolate,O-ethyl-O-(4-chlorophenyl)-S-n-propyl-phosphorothionothiolateO-ethyl-O-(2,4-dichlorophenyl)-S-n-propyl-phosphorothionothiolate,O-ethyl-O-(2,4,5-trichlorophenyl)-S-n-propyl-phosphorothionothiolate,O-ethyl-S-(4-chlorophenyl)-S-n-propyl-phosphorothionodithiolate.